Polymers of 9, 10-epoxyoctadecanol and processes for their preparation



PatentedDecas, 1948 ronmns F alo-uroxroc'ranucmon AND mocussus ron THEIR PREPARA- TION Daniel 5...... and Geraldine N. Blllen, Philade phia, Pa., assiznors' to the United States of America as represented by the Secretary of Agriculture Np Drawing. Application September 27, 1946,

Serial No. 699,647

(Granted under the act of March 3, 1883, as amended April 30, 1928; 370 Q. G. 757) 17 Claims.

This application is made under the act of March 3, 1883, as amended by the act of April 30, 1928, and the invention herein described, if patented, may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment to us of any royalty thereon.

This invention relates to polymeric compounds,

and more particularly, to compounds formed bythe polymerization of 9,10-epoxyoctadecanols, and it has among its objects the provision of new compositions of matter, namely, polymerized 9,10 epoxyoctadecanols, together with processes for their preparation. Other objects and advantages will be apparent from the description of the invention.

We have found that 9,10-epoxyoctadecanols, which contain an oxirane ring, that is, the atomic grouping and which are compounds represented by the following formula undergo polymerization when subjected to heat treatment.

The 9,10-epoxyoctadecanols are difunctional compounds containing both theoxirane ring and a hydroxyl group within the same molecule, and it appears likely, therefore, that on polymerization, long-chain, polyether type compounds are formed wherein the recurring structural units may be linked to either the ninth optenth carbon atom of the monomer radicals, as illustrated, for example, by the following mechanism which shows linkage to the tenth carbon atom:

HOH HOH HDH 1191 lHili (+112): CHaOH H3 CH:

, etc.

In general, the structure of the resulting products may be illustrated by the following generic formula:

HaOH Ha wherein X and Y together may represent an oxirane oxygen as, for example, in the formation of the dimer. Or, X may represent a hydroxy radical, in which event Y will represent a radical of the formula wherein X and Y will have the same significance as above, the products being polymers of higher order than the dimer.

The two stereoisomeric 9,10-epoxyoctadecanols having melting points of 54 and 48 (3., respectively, and whichmay be used singly or in combination for the production of polymers in accordance with our invention, can be prepared by various methods. For example, these 9,10-epoxyoctadecanols can be prepared by epoxidizing oleyl alcohol (cis-9,10-octadecano1) and elaidyl alcohol (trans-9,10-octadecanol) with perbenzoic acid in acetone solution in the manner described by Swern in his application filed December 8, 1944, Serial No. 567,297, now patent No. 2,411,762. As illustrative of the preparation of the 9,10-epoxyoctadecanol having a melting point of 54 C., the afore-mentioned Swern process can be carried out as follows:

To 3140 ml. of an acetone solution containin 138 grams of perbenzoic acid, there is added, at.

0 to 5 0., 274 grams of oleyl alcohol. The solution is then allowed to stand for about 40 hours at room temperature and is then cooled to approximately -25 C. The precipitate thus obtained, comprising mainly 9,10-epoxyoctadecanol, is filtered oil and dried, yielding 247 grams of a material that melts at 54 to 55.5 C.

The 9,10-epoxyoctadecanols can also be prepared by epoxldizlng' the respective clsor trans-9,10-octadeceno1 with peracetic acid in acetic acid solution; according to the process of the refractive index taken at 60 C. for the yellow sodium line Gulf). The results obtained are shown in the following tabulation of the experimental data:

Monomer used 9,10-Epoxyoctedecanoi, M. P. 64 0. 9,10-Epoxyoctadecanol, M. P. 48 C.

Zt'iiififiiiffifi'ii Oxirane Oxirane Oxirane I Oxirane Time in hours Oxygen, lnlp Oxy en, [nb Oxy en, [1111) Oxy en, [1i]p Per ent Per ent Per ent Per cut 5. 5 1.445 5. 5 1. 445 5. 6 1. 443 5. 6 l. 443 4.6 1. 450 4.6 1. 4.50 4. 5 l. 447 4. 8 1. 448 4. 3 1. 451 4. 2 1. 450 4. 6 1. 44B 4. 3 1. 449 3. 5 l. 453 3. 0 1. 454 4. 2 1. 450 3. 7 1. 451 2. 4 1. 456 1. 4 1. 459 3. 3 1. 453 2. 2 l. 456 0.3 1.463 0.0 1. 462 2.3 1.457 0.3 1.464 0.0 1.453 0.3 1.464 0. 2 1.464

elaidyl alcohol, while maintaining the temperature of the reaction mixture at approximately room temperature by means of external cooling. Stirring is continued for about 5 hours at room temperature. The reaction mixture is then diluted with ice water, filtered, and the precipitate, comprising mainly 9,10-epoxyoctadecanol, is washed free of acetic acid. There is obtained 69 grams of 9,10-epoxyoctadecanol which, on recrystallization from acetone, melts at 48 C.

According to the process of the invention, a 9,10-epoxyoctadecanol is heated at a polymerizing temperature of about from to 200 0., preferably about from 90 to 100 C., until a polymer, having an oxirane oxygen content below the oxirane oxygen content of the starting 9,10- epoxyoctadecanol, is produced.

The rate of the polymerization reaction may be accelerated by subjecting the 9,10-epoxyoctadecanols to heat treatment in the presence of polymerization catalysts which may be either alkaline catalysts, such as sodium hydroxide, sodium methylate, and trimethylamine, or acidic catalysts such as sulfuric acid and naphthalenefl-sulfonic acid. We prefer to use an acidic polymerization catalyst such as naphthalene-psulfonic acid because it is readily dispersible in the solid monomers, is miscible with the molten monomers as well as with the polymeric reaction products, does not adversely afiect the color of the polymeric material, and is readily removed therefrom by extraction with water.

As an illustrative embodiment of a manner in which our invention may be carried out in practice, the following example is given:

Approximately 2 percent, by weight, of naphthalene-fi-sulfonic acid is intimately and separately mixed with the 9,1o-epoxycctadecanols hav-' ing melting points of 54 and 48 C., respectively. The respective mixtures so obtained are heated in a constant temperature bath until polymerization is complete, as indicated by periodic analyses for oxirane oxygen, for example, according to the method described by Nicolet and, Poulter (J. Am. Chem. Soc. 52, 1186 (1930)),and determination The viscosity of the treated materials gradually increases as the polymerization proceeds. The polymeric products obtained under identical conditions from the two stereoisomers of, the 9,10- epoxyoctadecanols are substantially alike, and depending upon the degree of polymerization, are colorless to pale yellow viscous oils or semi-solid products having the consistency of petrolatum. The polymerized products are insoluble in water and petroleum naptha (hexane fraction), and are soluble in diethyl ether, ethanol, propanol, ethyl acetate, ethylene dichloride, benzene, acetone, and methyl ethyl ketone.

The polymerization process may be continued until the oxirane oxygen content of the polymeric material has been reduced to below about 0.2 percent, or interrupted at any intermediate stage, depending upon the desired properties of the final product.

The polymerization catalyst can be elminated from the polymerized material by dissolving the latter in a suitable water-immiscible solvent, such as benzene or diethyl ether, and then washing the solution so obtained with water or aqueous alkali.

The products obtainable by polymerization of 9,10-epoxyoctadecanols are stable toward hydrolysis and possess properties which render them useful as plasticisers, as components of cosmetics and creams, and as viscosity-index improving agents for lubricants.

Since these polymers still contain hydroxy groups, they are capable of undergoing reactions typical of compounds containing such a group. Thus, for example, they yield esters with acids, and on treatment with sulfating agents, they are converted into compounds possessing surfaceactive properties.

Although we prefer to conduct the polymerization process at a temperature of about from to C., the temperature conditions may vary considerably to suit the size of the batch and the nature of the final product. Satisfactory results may be attained within a temperature range of about from 55 to 200 C. In general, lower temperatures and polymerization in the absence of a catalyst decrease the rate of the polymerization process.

In the operation of the process, it is not necessary to utilize highly purified monomers. Thus, satisfactory polymers can be obtained by using as the starting material the products obtained by epoxidation of the 9,10-octadecanols without subjecting these materials to recrystallization.

Having thus described our invention, we claim: an oxirane oxygen content of 5.5 percent at a 1. A compound of the general formula polymerizing temperature or about from 90 to om-(orm -on- /O-OHr-(OH1)1 on- O CH -(CH;) on

I o H- on 11- on n 91 (53!)! (471m! CHiOH ()H: v n 43H:

where n is zero or any integer. K 100 C. in the presence of naphthalene-p-sulfonic 2. A polymerized 9,10-epoxyoctadeo8-nol having acid until a polymer having an oxirane oxygen an oxirane oxygen content below that of the content substantially below 5.5 percent is monomeric 9,10-epoxyoctadecanol. 1 produced.

3. A polymerized 9,10-epoxyoctadecanol having 13. A process comprising heating a 9,10-epoxyan oxirane oxygen content of not more than about octadecanol having a melting point of 54 C. and 0.3 percent. an oxirane oxygen contentof 5.5 percent at a 4. Apolymerized 9,10-epoxyoctadecanol having polymerizing temperature of about from 90 to an oxirane oxygen content below that of the :0 100 C. in the presence of naphthalene-p-sulfonic monomeric 9,10-epoxyoctadecanol, and having acid until a polymer having an oxirane oxygen an index of refraction taken at 60 C. with the content of not more than about 0.3 percent is yellow sodium line above that of the monomeric produced. 9,10-epoxyoctadec'anol. 14. A process comprising heating a 9,10-epoxy- 5. A polymerized 9,10-epoxyoctadecanol having octadecanol having a melting point of 48 C. and an oxirane oxygen content of not more than an oxirane oxygen content of 5.6 percent at polyabout 0.3 percent, and having an index of refracmerizlng temperature until a polymer having an tion taken at 60 C. with the yellow sodium line of oxirane oxygen content substantially below 5.6 not less than 1.462. percent is produced.

'6. A process comprising heating a 9,10-epoxy- 15. A process comprising heating a 9,10-epoxyoctadecanol at'polymerizing temperature until a octadecanol having amelting point of 48 C. and

' polymer having an oxirane oxygen content below. an oxirane oxygen content of 5.6 percent at a that of the 9,10-epoxyoctadecanol is produced. polymerizing temperature of about from 90 to 7. A process comprising heating a 9,10-epoxy- 100 C'. until a polymer having an oxirane oxygen octadecanol at a polymerizing temperature of content substantially below 5.6 percent is proabout from 55 to 200 C. until a polymer'having duced. an oxirane oxygen content below that of the 16. Aprocess comprising heatinga 9,10-epoxy- 9,10-epoxyoctadecanol is produced. octadecanol having a melting point of 48 C. and v8. A process comprising heating a 9,10-epoxyan oxirane oxygen content of 5.6 percent at a octadecanol at a polymerizing temperature of 40 polymerizing temperature of about from 90 to about from 90 to 100 C. until a polymer having 100 C. in the presence of naphthalene-fl sulfonic an oxirane oxygen content below that of the] acid untila polymer havinga ir n g n- 9,l0-epoxyoctadecanol is produced. tent substantially below 5.6 percent is produced.

9 A process comprising heating a 9,10-epoxy- 1'1. A process comprising heating a 9,10-epoxy octadecanol at a polymerizing temperature in the octadecanol having a melting point of 48 C. and presence of naphthalene-p-sulfonic acid until a an oxirane oxygen content of 5.6 percent at a polymer having an oxirane oxygen content below polymerizing temperature of about from 90 to that of the 9,10-epoxyoctadecanol is produced. 100 C. in the presence of naphthalene-p-sulfonic 10. A process comprising heating a 9,10-epoxyacid until a polymer havingan oxirane oxygen octadecanol having a. melting point of 54 C; and content of not more than about 0.3 percent is an oxirane oxygen content of 5.5 percent at 9018- P c d merizing temperature until a polymer having an DANIEL SWERN. oxirane oxygen content substantially below 5.5 4 GERALDINE N. BIL-LEN. percent is produced. 11. A process comprising heating a 9,10-epoxy- 55 REFERENCES CITED octadecanol having a mel in p int of 54 C. an The following references are of record in the an oxirane oxygen content or 5.5 percent at a tile of this patent: polymerizing temperature of'about from to C. until a polymer having an oxirane oxygen UNITED STATES PATENTS content substantially below 5.5 percent is Number N m Date produced. 1,641,710 Untiedt Sept. 6, 1927 12. A process comprising heating a 9,10-epoxy- 1,921,378 Webel Aug. 8, 1933 octadecanol having a melting point oi 54 C. and v 2. 41.702 Eatough y 26. 19 

